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Understanding the dynamics of excited-state vibrational energy relaxation in photosynthetic pigments is crucial for elucidating the mechanisms underlying energy transfer processes in light-harvesting complexes. Utilizing advanced femtosecond broadband transient fluorescence (TF) spectroscopy, we explored the excited-state vibrational dynamics of Chlorophyll-a (Chl-a) both in solution and within the light-harvesting complex II (LHCII). We discovered a vibrational cooling (VC) process occurring over â¼6 ps in Chl-a in ethanol solution following Soret band excitation, marked by a notable ultrafast TF blueshift and spectral narrowing. This VC process, crucial for regulating the vibronic lifetimes, was further elucidated through the direct observation of the population dynamics of higher vibrational states within the Qy electronic state. Notably, Chl-a within LHCII demonstrated significantly faster VC dynamics, unfolding within a few hundred femtoseconds and aligning with the ultrafast energy transfer processes observed within the complex. Our findings shed light on the complex interaction between electronic and vibrational states in photosynthetic pigments, underscoring the pivotal role of vibrational dynamics in enabling efficient energy transfer within light-harvesting complexes.
RESUMO
Graphite is a widely used anode material in commercial lithium-ion batteries (LIBs), but its low theoretical specific capacity and extremely low redox potential limit its application in high-performance lithium-ion batteries. However, developing lithium-ion battery anode with high specific capacity and suitable working potential is still challenging. At present, conductive polymers with excellent properties and graphite-like structures are widely used in the field of electrochemistry, but their Li+ storage mechanism and kinetics are still unclear and need to be further investigated. Therefore, we synthesized the conducting polymer Fe3(2, 3, 6, 7, 10, 11-hexahydroxytriphenylene)2 (Fe-CAT) by the liquid phase method, in which the d-π conjugated structure and pores facilitate electron transfer and electrolyte infiltration, improving the comprehensive electrochemical performance. The Fe-CAT electrode displays a high capacity of 950 mA h g-1 at 200 mA g-1. At the current density of 5.0 A g-1, the electrode shows a reversible capacity of 322 mA h g-1 after 1000 cycles. The average lithiation voltage plateau is â¼ 0.79 V. The combination of ex-situ characterization techniques and electrochemical kinetic analysis reveals the source of the excellent electrochemical performance of Fe-CAT. During the charging/discharging process, the aromatic ring in the organic ligand is involved in the redox reaction. Such results will provide new insights for the design of next-generation high-performance electrode materials for LIBs.
RESUMO
The bulk-boundary correspondence is a critical concept in topological quantum materials. For instance, a quantum spin Hall insulator features a bulk insulating gap with gapless helical boundary states protected by the underlying Z2 topology. However, the bulk-boundary dichotomy and distinction are rarely explored in optical experiments, which can provide unique information about topological charge carriers beyond transport and electronic spectroscopy techniques. Here, we utilize mid-infrared absorption micro-spectroscopy and pump-probe micro-spectroscopy to elucidate the bulk-boundary optical responses of Bi4Br4, a recently discovered room-temperature quantum spin Hall insulator. Benefiting from the low energy of infrared photons and the high spatial resolution, we unambiguously resolve a strong absorption from the boundary states while the bulk absorption is suppressed by its insulating gap. Moreover, the boundary absorption exhibits strong polarization anisotropy, consistent with the one-dimensional nature of the topological boundary states. Our infrared pump-probe microscopy further measures a substantially increased carrier lifetime for the boundary states, which reaches one nanosecond scale. The nanosecond lifetime is about one to two orders longer than that of most topological materials and can be attributed to the linear dispersion nature of the helical boundary states. Our findings demonstrate the optical bulk-boundary dichotomy in a topological material and provide a proof-of-principal methodology for studying topological optoelectronics.
RESUMO
Metal tellurides (MTs) have emerged as highly promising candidate anode materials for state-of-the-art lithium-ion batteries (LIBs) and sodium ion batteries (SIBs). This is owing to the unique crystal structure, high intrinsic conductivity, and high trap density of such materials. The present work delivers a detailed discussion on the latest research and progress associated with the use of MTs for LIBs/SIBs with a focus on reaction mechanisms, challenges, electrochemical performance, and synthesis strategies. Further, the prospects and future development of MT anode materials are discussed in terms of strategies to overcome the existing limitations. This review provides both an in-depth understanding of MTs and provides the driving force for expanding research on MTs for energy storage and conversion applications.
RESUMO
Two-dimensional (2D) transition-metal dichalcogenide materials show potential for use in alkali metal ion batteries owing to their remarkable physical and chemical properties. Nevertheless, the electrochemical energy storage performance is still impaired by the tendency of aggregation, volume, and morphological change during the conversion reaction and poor intrinsic conductivity. Until now, ultrathin molybdenum disulfide nanosheets with a metallic-phase structure on the inner surface of mesoporous hollow carbon spheres (M-MoS2@HCS) have rarely been investigated as an anode for sodium-ion batteries. In this work, a novel M-MoS2@HCS anode was designed and synthesized by employing a template-assisted solvothermal reaction. Structural and chemical analyses indicate that the M-MoS2 nanosheets with a larger interlayer spacing compared to their semiconductor counterpart grow on the inner surface of HCS via covalent interactions. When used as the anode materials for Na+ storage, the M-MoS2@HCS anode presents durable and rapid sodium storage properties. The developed electrode shows a reversible capacity of 291.2 mAh g-1 at a high current density of 5 A g-1. After 100 cycles at 0.1 A g-1, the reversible capacity is 401.3 mAh g-1 with a capacity retention rate of 79%. After 2500 cycles at 1.0 A g-1, the electrode still delivers a reversible capacity of 320.1 mAh g-1 with a capacity retention rate of 75%. The excellent sodium storage capability of the MoS2@HCS electrode is explained by the special structural design, which reveals great potential to accelerate the practical applications of transition-metal dichalcogenide electrodes for sodium storage.
RESUMO
Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300-1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10(-5)M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 µJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process.
RESUMO
We report an improved setup of femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy (FNOPAS) with a 210 fs temporal response. The system employs a Cassegrain objective to collect and focus fluorescence photons, which eliminates the interference from the coherent photons in the fluorescence amplification by temporal separation of the coherent photons and the fluorescence photons. The gain factor of the Cassegrain objective-assisted FNOPAS is characterized as 1.24 × 10(5) for Rhodamine 6G. Spectral corrections have been performed on the transient fluorescence spectra of Rhodamine 6G and Rhodamine 640 in ethanol by using an intrinsic calibration curve derived from the spectrum of superfluorescence, which is generated from the amplification of the vacuum quantum noise. The validity of spectral correction is illustrated by comparisons of spectral shape and peak wavelength between the corrected transient fluorescence spectra of these two dyes acquired by FNOPAS and their corresponding standard reference spectra collected by the commercial streak camera. The transient fluorescence spectra of the Rhodamine 6G were acquired in an optimized phase match condition, which gives a deviation in the peak wavelength between the retrieved spectrum and the reference spectrum of 1.0 nm, while those of Rhodamine 640 were collected in a non-optimized phase match condition, leading to a deviation in a range of 1.0-3.0 nm. Our results indicate that the improved FNOPAS can be a reliable tool in the measurement of transient fluorescence spectrum for its high temporal resolution and faithfully corrected spectrum.